Insecticidal and fungicidal spray oil



Patented July 17, 1951 UNITED} STATES PATENT orricc INSECTICIDAL AND FUNGICIDAL SPRAY OIL Clifford J. Boissonou, Concord, and'Wallace J. Yates, Martinez, Calif., assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application April 27, 1948,

Serial No. 23,614 I 4 Claims. 1

This invention relates to insecticidal and fungicidal horticultural spray oil compositions and to aqueous emulsions thereof.

One of the problems of the prior art has been the difficulty of efiecting and maintaining proper dispersion of plant-treating agents in spray oil emulsions. The use of many emulsifiers, such as cresols, in petroleum hydrocarbon spray oils has the disadvantage of being effective in emulsifying and removing the protective vegetable wax coatings of plants, thereby causing serious plant injury.

An object of this invention is to provide an emulsifiable spray oil composition capable of effecting and maintaining proper dispersion of an added plant-treating agent in aqueous emulsions thereof. Another object is to provide an emulsifiable hydrocarbon spray oil composition which will not have a deleterious effect on the protective vegetable wax coatings of plants. Other objects will be apparent as the description proceeds.

It has now been discovered that the above and other objects may be attained by a composition comprising a predominant amount of a horticultural hydrocarbon spray oil and a minor but emulsifying and depositing amount therefor of a combination or mixture of an oil-soluble alkyl phenol and certain higher molecular weight open-chain aliphatic carboxylic ester emulsifiers, as hereinafter defined. As one of its functions, the allwl phenol is-a mutual solutizer for the spray oil and said ester.

Described generally, the aforesaid ester emulsifier is a mono-ester of a polyalkylene glycol having from about 14 to about 60 carbon atoms and of a fatty earboxylic acid having from about 12, and preferably from about 16, up to about 30 carbon atoms. Preferably the polyalkylene glycol portion of said ester hasfrom about 14 up to about 30 carbon atoms.

The polyalkylene glycol portion or residue of the emulsifier esters contains recurring alkylene (oxyalkylene) radicals having from two to about six carbon atoms each,- inclusive, and it may be a di-, tri-, tetra-, etc., alkylene glycol residue, as for example from octa-ethylene glycol, di-octylene glycol, tri-hexylene glycoLetc.

Various fatty acids may be utilized to supply the acid radical of the esters, but the unsaturated fatty acids are preferable. Thus, preferably at least 20 per cent by weight of the ester or ester mixture is of an unsaturated fatty acid. Illustrative suitable unsaturated fatty acids are: delta-9,10-dodecylenic, palmitolenic, oleic, azelaic, iso-oleic, gadoleic, arachidonic, petroselic, erucip, and cetoleic acids. Particularly effective and outstanding is a mixture of oleate esters of hexaethylene glycol, of octaethylene glycol and of decaethylene glycol containing a predominant proportion of the latter two esters.

The alkyl phenols used in the preparation of the compositions of this invention are oil-soluble substances. They are mutual solutizers for, and co-acting emulsifying, wetting and spreading aids with, the aforesaid ester emulsifiers. They have molecular weights of preferably up to about 250. Other polar groups than the phenolic hydroxyl, such as amino and nitro groups, may also be present in the alkyl phenols. Examples of effective alkyl phenols include the various cresols, thymol, carvacrol, p-octyl and p-butyl phenols, butyl nitro phenols, propyl amino phenols, nitro cyclohexyl phenols, dinitro lower alkylated phenols, etc.

The optimum amount of a given alkyl phenol to be employed in the compositions depends upon various variable factors of a given application. The amount is readily adjusted according to the artisans skill in the light of the present disclosures. In general, as a guide, from about 0.05 wt. percent to about 0.5 wt. percent of an alkyl phenol, based on the amount of spray oil, is suitable. In most cases from 0.1 wt. percent. to 0.3 wt. percent of an alkyl phenol is preferred. Larger or smaller proportions may be used. Further, and as a general guide, the amount of alkyl phenol is selected to range from about'one-third to about twice the weight of the ester emulsifier employed.

time of each insecticidal emulsion in the spray machine of 30 seconds; spray nozzle orifice diameter of /64 inch; distance of nozzle to target of orange tree leaves of six feet; and spraying time of 6 seconds. When calculated on the basis of a hundred gallons of finished emulsion, there was employed for each emulsion two ounces of a water-conditioner or water-soluble spreader made up of the commonly used conventional twenty weight per cent casein with eighty weight per cent sodium carbonate.

TABLE I Materials in light medium spray oil in per cent by vol.:

Agent A of invention 3. 3 0. 4 0. 5 0. 5 0. 4 Solutizer-cr 0.2 0. 2 0. 3 Results therefrom: Observed oil deposit and oil spread on orange tree foliage. good good good poor poor Materials in light medium spray oil in per cent by vol.:

Saturated cocoanut fatty acid esters of trito penta-ethylene glycol. 04 0.5 0. 4 0. l5 3 Solutizer:

Crawls 0.2 0.2 .2 .l Dioctyl sodium fn fl 0. 0 1 Results therefrom:

Observed oil deposit and oil spread on orange tree i0liage poor poor poor poor poor poor 1 A mixture of mono-oleate esters of hexaethylene glycol, of octaethylene glycol, and of decaethylene glycol in which the latter two predominate.

The present horticultural spray base oils include those known to the artfor use in spray oil emulsions. They are usually substantially free from unsaturated and aromatic hydrocarbons known to be injurious to plant tissues. Summer spray oils usually have viscosities ranging from about 40 to about 300 seconds Saybolt at 100 F. Dormant winter spray oils usually have viscosities ranging from about 70 to about 300 seconds Saybolt at 100 F. and have from about 50% to about 95% unsulfonatable residue, low sulfonatable residue type of mineral spray oils being preferred.

The resent emulsifiable compositions may have incorporated therewith, either when alone or in aqueous emulsion, an effective quantity of a solid horicultural plant-treating substance, such as plant-growth promoters, plant deficiency correctives, fungicides and insecticides.

An example of a formulation of the present for summer use is as follows:

In general, each gallon of the spray oil composition is used, emulsified in from about 50 to about 2000 gallons of water, with or without the incorporation of other materials, including water-soluble spreaders, as are well understood in the art.

Comparative oil spread and oil deposit tests on orange tree leaves by a standardized procedure were made with spray oil emulsions with and without the present emulsifier combinations, and with other emulsifier combinations, the results of which are given in Table 1. Conditions used for these spraying tests were: oil concentration of 1.67% by volume of water used (5 volumes oil to 300 volumes water) water hardness in parts per million (P. P. M.) of calcium carbonate was 150; water temperature of 75 F.; pressure in spray machine of 500 lbs. per sq. inch gage; circulation In an orchard test of the present invention, Valencia orange trees were sprayed with an aqueous emulsion (water continuous phase) of an illustrative composition of this invention composed of a light medium mineral spray oil having a Saybolt universal viscosity of 70 seconds at F. and a 92% unsulfonatable residue, and containing 0.5% by vol. (based on the oil) of monooleate esters of a polyethylene glycol, which glycol had from about seven to about twelve ethylene glycol units (i. e. oxyethylene units) therein, and 0.3% by vol. (based on the oil) of cresols. The results from these orchard trials were found to be: emulsification was excellent and the observed oil deposit and oil spread on orange tree foliage in the orchard was excellent. Subsequent inspection for insecticide control showed that excellent control of red scale was obtained; there was no serious injury to the thus-sprayed orange tree foliage.

Proper dispersion of an added toxic agent, and of the spray oil, generally termed compatibility, in emulsions prepared in accordance with the invention, is shown by illustrative embodiments thereof as described hereinafter. An ester emulsifier of the invention was obtained by esteriflcation condensation of stoichiometric molal quantitles of high molecular weight fatty mono-carboxylic acids, including at least about twenty per cent by weight of oleic acid, with a mixture of hexaethylene glycol, octaethylene glycol and decaethylene glycol. The fatty acids and the polyalkylene glycols may be heated together thereby driving off water with or .without the use of a catalyst in methods well known to the art. The resultant mixture of fatty acid mono-esters of said polyethylene glycols, termed agent B, was tested for compatibility and compared under comparable conditions with a representative prior art emulsifier, agent C. The tests were made under the same operating conditions as described hereinbefore with reference to the other tests. Agent C was a mixture of 0.75 part of saturated cocoanut fatty acid mono-esters of tri-, tetra-, and penta-ethylene glycols, 0.25 part of dioctyl sodium sulfo-succinate, 1.6? parts of sodium petroleum mahogany sulfonates and 3.33 parts of cottonseed oil. Other details and the results are given in Table II.

TABLE II Compatibility of medium spray oil formulations with sodium fluoaluminate and zinc oxide Materials Added to Spray Oil,

Per Cent by Vol.:

'A gent B of inventmn. Cresols Comparative Agent 0. Plant-Treating Agents in Lbs. Per 100 Gals. moi Finished Oil-In-Water Spray:

Sodium Fluoaluminat Zinc Oxide.. Water Conditioner in Ounces Per 100 Gals. of Finished Oil-In-Water Spray: Bentonite Results on Compatibility upon Emulsification:

Free 01] Mediumamount. None Extreme None M0derate... None.

. Extreme Very s1ight. Mediumamount. Mediumamount. Extreme Voryslight.

g Mediumamount. None None None Moderate." None.

Sticking to Tank Slight do do -.d0 None Do.

From the data in Table II, it is seen that the use of agent B of this invention provided superior results in at least one or more of the important criteria of compatibility over results obtained with agent C. Agent B substantially eliminated extreme, i. e. excessive and impractical flocculation of the added plant-treating agents, and also eliminated excessive separation of free oil from the emulsion.

Similar compatibility tests were also conducted with basic copper sulfate, and also with Bordeaux mixture. Details and results are summarized in Table III.

TABLE III Compatibility of heavy dormant spray oil formulations with copper compounds Materials Added to Spray Oil, Per Cent by Volume of the Oil:

Emulsifler Agent B 0.4 0.4.

Cresols. 0.4 0.4.

Agent D 0.85 0.85 Agiled Toxic Agent Per 100 Gals. of Finished Oil-l'n-Water pray:

Basic Copper Sulfate Obs.) 6 6 Bordeaux mixture (lbs.) 16 16. Results on Compatibility upon Emulsiflmiion:

Free Oil. None None None None.

flocculation"- Extreme .do. Extreme Do.

Scumming Slight do N one Do.

Sticking to Tank do do. Slight Do.

1 Agent D was a mixture of 3 parts of saturated cocoanut fatty acid mono-esters of tri-,

ethylene glycols and 1 part of dioctyl sodium sulfo-succinate.

9 Contains of copper. 3 Containing 22% of copper.

tetra-, and penta- 4 Flocculated precipitate was the size of bird-shot, excessive and unsatisfactory.

In addition to the compatibilities with toxic agents noted above, other tests have shown that the present compositions also have excellent compatibility with DDT powders and similar organic toxicants in emulsion form and with limesulfur mixtures.

We claim as our invention:

1. A water-emulsifiable insecticidal spray oil composition comprising a predominant amount of a light medium mineral spray oil having a Saybolt universal viscosity of about '70 seconds at 100 F. and having an unsulfonatable residue of about 92 said all having dissolved therein about 0.5% by volume of monooleate esters of a polyethylene glycol having from about '7 to about 12 oxyethylene units, said esters being solubilized in said oil by about 0.3% by volume of oil-soluble unsubstituted cresols.

2. A water-emulsifiable insecticidal spray oil composition comprising a predominant amount of a horticultural hydrocarbon spray oil having dissolved therein between about 0.05% and about 2% by volume of an unsaturated fatty acidmonoester of a polyalkylene glycol and a solubilizing amount of an oil-soluble unsubstituted alkyl 12 and about 30 carbon atoms in the acid portion.

4. A water-emulsifiable spray oil composition comprising a predominant amount of a horticultural hydrocarbon spray oil having dissolved REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,121,039 Mills June 21, 1938 2,162,904 Allison June 20, 1939 OTHER REFERENCES Chemicals by Glyco 1944) published by Glyco Products Co., Inc., Brooklyn, N. Y., pp. 13, 17-23. 

3. A WATER-EMULSIFIABLE INSECTICIDAL SPRAY OIL COMPOSITION COMPRISING A PREDOMINANT AMOUNT OF A HORTICULTURAL HYDROCARBON SPRAY OIL HAVING DISSOLVED THEREIN BETWEEN ABOUT 0.01% AND ABOUT 5% BY VOLUME OF A FATTY ACID MONOESTER OF A POLYALKYLENE GLYCOL AND A SOLUBILIZING AMOUNT OF AN OIL-SOLUBLE UNSUBSTITUTED ALKYL PHENL, SAID ESTER HAVING BETWEEN ABOUT 14 AND ABOUT 60 CARBON ATOMS IN THE GLYCOL PORTION AND BETWEEN ABOUT 12 TO 30 CARBON ATOMS IN THE ACID PORTION. 